CN114057966A - Block copolymer elastomer, preparation method thereof and modified asphalt - Google Patents
Block copolymer elastomer, preparation method thereof and modified asphalt Download PDFInfo
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- CN114057966A CN114057966A CN202010766634.3A CN202010766634A CN114057966A CN 114057966 A CN114057966 A CN 114057966A CN 202010766634 A CN202010766634 A CN 202010766634A CN 114057966 A CN114057966 A CN 114057966A
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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
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
- C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
- C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
- C08F297/044—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes using a coupling agent
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L95/00—Compositions of bituminous materials, e.g. asphalt, tar, pitch
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The invention provides a block copolymer elastomer, a preparation method thereof and modified asphalt. The block copolymerization elastomer has a structural formula of PS-SB-PB-SB-PS, wherein PS is a styrene segment, SB is a styrene-butadiene random segment, PB is a butadiene segment, and the mass ratio of PS, SB and PB is 35-45:1-5: 50-64. The block copolymer elastomer with a certain structure is obtained by using styrene and butadiene as raw materials and controlling the composition and the proportion of the raw materials. The block copolymerization elastomer can be independently used as a modifier to modify asphalt, so that the softening point of high-grade asphalt at high temperature is greatly improved, and the indexes of the high-grade asphalt meet the requirements of related products in waterproof elastomer (SBS) modified asphalt (GB/T26528-2011).
Description
Technical Field
The invention belongs to the technical field of polymer synthesis, and particularly relates to a block copolymer elastomer, a preparation method thereof and modified asphalt.
Background
The asphalt is a waterproof, moistureproof and anticorrosive organic cementing material and can be mainly divided into coal tar asphalt, petroleum asphalt and natural asphalt, wherein the coal tar asphalt is a coking byproduct. Petroleum pitch is the residue of crude oil distillation. Natural bitumen is stored underground, and some forms a mineral layer or is accumulated on the surface of the crust. The asphalt is mainly used in the industries of paint, plastics, rubber and the like and pavement and the like. In order to obtain better asphalt properties, it is necessary to modify the asphalt by incorporating modifiers such as rubber, resin, high molecular weight polymer, ground rubber powder, etc. into the asphalt or by taking measures such as mild oxidative processing of the asphalt to improve the properties of the asphalt or asphalt mixture.
Patent CN109957254A discloses a preparation method of SBS modified asphalt, which mainly comprises the following steps: the invention relates to a method for preparing modified asphalt, which comprises the steps of raw material treatment, cosolvent addition, modifier addition, development and curing, wherein Clarity 90# asphalt and Tahe petrochemical 60# asphalt are used as matrix asphalt to prepare the modified asphalt capable of solving the problems of product index attenuation and service performance change of the asphalt in the process of long-distance and long-time heating and transportation.
Patent CN106751950A discloses a preparation method of SBS modified asphalt, which also adds polyvinyl alcohol, stearic acid, sodium hydroxide, dibutyl phthalate, sodium chloride, zinc oxide, tetramethyl thiuram disulfide, light magnesium oxide, dioctyl phthalate and other various additives for modification to obtain a modified asphalt with good flexibility, high bending strength and high compressive strength.
However, the modification of asphalt in the prior art is mostly based on low-grade asphalt with the grade less than 100#, and in order to obtain better modification effect, an elastomer prepared by mixing various components needs to be added, and the preparation of a single modifier for high-grade (such as 100#, 200#) asphalt is rarely related. However, high-grade asphalt has wide application in the fields of waterproof materials, pavement applications and the like.
Therefore, it is urgently needed to provide a modifier applied to high-grade asphalt to improve the performance of the high-grade asphalt and enable the high-grade asphalt to meet the indexes of related product requirements in waterproof elastomer (SBS) modified asphalt (GB/T26528-2011).
Disclosure of Invention
The invention provides a block copolymer elastomer, which can be independently used as a modifier to modify asphalt by controlling the composition and the proportion of raw materials, so that the softening point of high-grade asphalt at high temperature is greatly improved, and the indexes of the relevant product requirements in waterproof elastomer (SBS) modified asphalt (GB/T26528-2011) are met.
The invention also provides a preparation method of the block copolymerization elastomer, which is simple and is beneficial to commercial production.
The invention also provides modified asphalt which has a higher softening point and can meet the indexes of related product requirements in waterproof elastomer (SBS) modified asphalt (GB/T26528-2011).
The invention also provides a preparation method of the modified asphalt, and the preparation method is simple to operate and low in cost.
The invention also provides application of the modified asphalt in the fields of waterproof materials and pavement application.
In a first aspect, the invention provides a block copolymer elastomer, the structural formula of which is PS-SB-PB-SB-PS, wherein PS is a styrene segment, SB is a styrene-butadiene random segment, PB is a butadiene segment, and the mass ratio of PS, SB and PB is 35-45:1-5: 50-64.
The block copolymer elastomer with a certain structure is obtained by using styrene and butadiene as raw materials and controlling the composition and the proportion of the raw materials. The block copolymerization elastomer can be independently used as a modifier to modify asphalt, so that the softening point of high-grade asphalt at high temperature is greatly improved, and the indexes of the high-grade asphalt meet the requirements of related products in waterproof elastomer (SBS) modified asphalt (GB/T26528-2011).
In a second aspect, the present invention provides a method for preparing the block copolymer elastomer, comprising the steps of:
under the condition of first anionic polymerization, styrene is subjected to polymerization reaction in an inert solvent to obtain a first product;
under the condition of second anionic polymerization, adding butadiene into the first product to perform polymerization reaction to obtain a second product;
and mixing and reacting the second product with a coupling agent, and then adding and mixing an antioxidant to obtain the block copolymerization elastomer.
According to the invention, the block copolymerization elastomer is prepared by adopting an anionic polymerization reaction through a three-section sequence control program, the preparation method is simple, and the industrial production is facilitated.
It will be appreciated that suitable polymerization conditions are more favorable to obtain a block copolymer elastomer of the desired structure. Specifically, the first anionic polymerization conditions include: carrying out polymerization reaction under inert atmosphere, wherein the polymerization reaction temperature is 35-55 ℃, the reaction pressure is 0.2-0.4MPa, the reaction time is 5-15min, and the initiator is organic lithium; the second anionic polymerization conditions include: carrying out polymerization reaction under inert atmosphere, wherein the polymerization reaction temperature is 35-55 ℃, the reaction pressure is 0.2-0.4MPa, and the polymerization reaction time is 10-30 min.
The invention adopts organic lithium as initiator to initiate anion polymerization reaction. The type of organolithium is not particularly limited and may be selected according to the reaction conditions, and may be, for example, at least one selected from n-butyllithium, sec-butyllithium, and tert-butyllithium.
The inert solvent in the present invention refers to a nonpolar solvent, that is, a solvent having a low dielectric constant. Such solvents do not undergo a proton autodelivery reaction nor do they solvate with the solute. They are mostly saturated hydrocarbons or benzene. The inert solvent is selected so long as it can achieve mixing of styrene and butadiene, and the inventors do not particularly limit this. For example, the inert solvent may be selected from one or more of C5-C8 alkanes or C5-C8 cycloalkanes.
The coupling agent and the antioxidant in the invention are all selected conventionally in the field, and can be prepared by self or purchased commercially. The inventors do not particularly limit this. For example, the antioxidant may be selected from long-acting antioxidants of type 1010, 1076, KW-1, KW-2, and TNPP and 565. The coupling agent can be silicon tetrachloride and the like.
In a third aspect, the invention provides a modified asphalt, which comprises the block copolymer elastomer and an asphalt matrix with the number of 100# -200 #.
In the modified asphalt, the block copolymerization elastomer is added into an asphalt substrate with the number of 100-200, and the block copolymerization elastomer is independently utilized to greatly improve the softening point of high-grade asphalt at high temperature, so that the modified asphalt meets the indexes of related product requirements in waterproof elastomer (SBS) modified asphalt (GB/T26528-2011).
The asphalt mark number in the invention refers to penetration degree, and the penetration degree of the asphalt is divided into 200, 160, 130, 110, 90, 70, 50, 30 and other marks according to the regulations of the national industry standard of people's republic of China, namely the technical Specification for constructing asphalt road surfaces.
Penetration is primarily a characteristic of the consistency of bitumen and is also used as a designation for bitumen. The method for testing the penetration comprises the following steps: the penetration depth of the sample into the asphalt sample, measured in 0.01mm, was determined in the laboratory by means of a penetrometer, i.e. a standard test cup containing a sample, in a water solution at 25 c, with a standard test needle weighing 100g, falling freely within 5 seconds.
In a fourth aspect, the present invention provides a method for preparing the modified asphalt, comprising the following steps: and melting the asphalt matrix, adding the block copolymer elastomer, rubber powder and filler, and mixing for reaction to obtain the modified asphalt.
As a specific embodiment of the invention, the mass ratio of the asphalt matrix to the block copolymer elastomer, the rubber powder and the filler is 60-70:5-10:10-20: 10-15. The filler in the present invention may be at least one selected from talc, calcium carbonate, fly ash, and the like, and is not particularly limited in the present invention.
It will be appreciated by those skilled in the art that suitable reaction conditions are more conducive to control of product properties. Specifically, the melting temperature is 160-180 ℃, the mixing reaction time is 5-8h, and the mixing reaction temperature is 160-180 ℃.
The preparation method of the modified asphalt has the advantages of simple operation and low cost. The modified asphalt prepared by the method has a higher softening point, and can meet the indexes of related product requirements in waterproof elastomer (SBS) modified asphalt (GB/T26528-2011).
In a fifth aspect, the invention provides an application of the modified asphalt in the fields of waterproof materials and pavement applications.
The block copolymerization elastomer with a certain structure is obtained by adopting styrene and butadiene as raw materials and controlling the composition and the proportion of the raw materials, and can be independently used as a modifier to modify asphalt, so that the softening point of high-grade asphalt at high temperature is greatly improved, and the high-grade asphalt meets the indexes of related product requirements in waterproof elastomer (SBS) modified asphalt (GB/T26528-2011). The preparation method of the block copolymer elastomer and the modified asphalt has the advantages of simple operation and low cost, and is beneficial to commercial production.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
FIG. 1 is a Gel Permeation Chromatography (GPC) spectrum of a block copolymer elastomer of example 1 of the present invention.
Detailed Description
The following detailed description of embodiments of the invention is intended to be illustrative, and not to be construed as limiting the invention.
The test standard for softening point in the present invention is GB/T4507.
The commercially available elastomer of the invention is purchased from the Zhongpetrochemical Yueyangbailing petrochemical with model YH 803;
the commercially available modified asphalt of the invention, designated 100# is obtained from medium fuel oil 100# asphalt.
The invention is described in detail below by means of specific examples:
example 1
Example 1 proposes a modified asphalt, the preparation method of which comprises the following steps:
(1) preparation of block copolymerized elastomers
Under the protection of high-purity nitrogen, 160g of styrene and 2000g of cyclohexane solvent are sequentially added into a 5L polymerization kettle, 6g of tert-butyl lithium is added after a polymerization system is deoxidized by the high-purity nitrogen, and polymerization reaction is carried out for 5-15min at the temperature of 50 ℃ and the pressure of 0.2MPa, so as to obtain styrene polymer solution.
Adding 240g of butadiene into the styrene polymer solution, and carrying out polymerization reaction for 10-30min at the temperature of 50 ℃ and under the pressure of 0.2-0.4MPa to ensure that reactants are completely polymerized.
Then, 0.3g of a silicon tetrachloride coupling agent was added to the polymerization reactor to continue the coupling reaction. After the coupling reaction is finished, 10g of antioxidant TNPP and 565 are added, wherein the mass ratio of TNPP to TNPP is 1: 1 to obtain a block copolymer elastomer after the mixture is subjected to water vapor coagulation, and obtaining a Gel Permeation Chromatography (GPC) spectrum of the block copolymer elastomer as shown in fig. 1, wherein the abscissa is time (min) and the ordinate is time-lapse refractive index. As can be seen from the figure, the GPC spectrogram of the product presents four-peak distribution which is respectively a macromolecular peak, an SBS peak, an SB section peak and a PS section peak, the molecular weight distribution is narrow, and the structure of the obtained product is PS-SB-PB-SB-PS.
(2) Preparation of modified asphalt
Taking 600g of asphalt with the number of 100#, melting at the temperature of 160-180 ℃, and then adding 60g of the block copolymer elastomer, 150g of rubber powder and 120g of talcum powder to react for 5 hours to obtain the modified asphalt.
Example 2
Example 2 provides a modified asphalt, the preparation method of which comprises the following steps:
(1) preparation of block copolymerized elastomers
Under the protection of high-purity nitrogen, 492g of styrene and 6000g of n-hexane solvent are sequentially added into a 15L polymerization kettle, 17g of sec-butyl lithium is added after a polymerization system is deoxidized by the high-purity nitrogen, and polymerization reaction is carried out for 5-15min at the temperature of 50 ℃ and under the pressure of 0.3MPa, so as to obtain styrene polymer solution.
708g of butadiene was added to the styrene polymer solution, and polymerization was carried out at 50 ℃ and 0.2 to 0.4MPa for 10 to 30min to complete the polymerization of the reactants.
Then, 0.9g of a silicon tetrachloride coupling agent was added to the polymerization vessel to continue the coupling reaction. After the coupling reaction is finished, 30g of antioxidant TNPP and 565 are added, wherein the mass ratio of TNPP to TN565 is 5:1, said mixture being coagulated with water vapor to obtain a block copolymer elastomer.
(2) Preparation of modified asphalt
Mixing the asphalt No. 90 with the asphalt No. 200 by 300g respectively, melting at 160-180 ℃, and adding 72g of the block copolymer elastomer, 150g of rubber powder and 120g of talcum powder to react for 5 hours to obtain the modified asphalt.
Example 3
Example 3 provides a modified asphalt, the preparation method of which comprises the following steps:
(1) preparation of block copolymerized elastomers
Under the protection of high-purity nitrogen, 1700kg of styrene and 25000kg of cyclopentane solvent are sequentially added into an industrial polymerization kettle, a polymerization system is deoxidized by the high-purity nitrogen, 37kg of n-butyl lithium is added, and polymerization reaction is carried out for 5-15min at the temperature of 40 ℃ and under the pressure of 0.4MPa, so as to obtain styrene polymer solution.
Adding 2550kg of butadiene into the styrene polymer solution, and carrying out polymerization reaction for 10-30min at the temperature of 50 ℃ and under the pressure of 0.2-0.4MPa to ensure that reactants are completely polymerized.
Then, 2.66kg of a silicon tetrachloride coupling agent was added to the polymerization vessel to continue the coupling reaction. After the coupling reaction is finished, adding 32kg of antioxidant TNPP and 565 in a mass ratio of 10:1, said mixture being coagulated with water vapor to obtain a block copolymer elastomer.
(2) Preparation of modified asphalt
240g of 90# asphalt and 360g of 160# asphalt are mixed and melted at the temperature of 160-180 ℃, and then 72g of the block copolymer elastomer, 120g of rubber powder and 120g of talcum powder are added to react for 5 hours to obtain the modified asphalt.
Comparative example 1
Comparative example 1 a modified asphalt was proposed, and comparative example 1 differs from example 2 in that comparative example 1 incorporates a commercially available elastomer into the modified asphalt, with the same procedure and parameters.
Comparative example 2
Comparative example 2 is a commercial modified asphalt, reference number 100 #.
The modified asphalt softening points of the respective examples and comparative examples were measured, and the results are shown in Table 1.
TABLE 1
As can be seen from Table 1, the modified asphalt prepared by using the block copolymer elastomer of the embodiment of the invention has a higher softening point, and meets the indexes of related product requirements in waterproof elastomer (SBS) modified asphalt (GB/T26528-2011).
In conclusion, the block copolymerization elastomer with a certain structure is obtained by using styrene and butadiene as raw materials and controlling the composition and the proportion of the raw materials, and can be independently used as a modifier to modify asphalt, so that the softening point of high-grade asphalt at high temperature is greatly improved, and the asphalt meets the indexes of related product requirements in waterproof elastomer (SBS) modified asphalt (GB/T26528-2011). The preparation method of the block copolymer elastomer and the modified asphalt has the advantages of simple operation and low cost, and is beneficial to commercial production.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. The block copolymerization elastomer is characterized in that the structural formula of the block copolymerization elastomer is PS-SB-PB-SB-PS, wherein PS is a styrene segment, SB is a styrene-butadiene random segment, PB is a butadiene segment, and the mass ratio of PS, SB and PB is 35-45:1-5: 50-64.
2. A process for producing a block copolymer elastomer according to claim 1, which comprises the steps of:
under the condition of first anionic polymerization, styrene is subjected to polymerization reaction in an inert solvent to obtain a first product;
under the condition of second anionic polymerization, adding butadiene into the first product to perform polymerization reaction to obtain a second product;
and mixing and reacting the second product with a coupling agent, and then adding and mixing an antioxidant to obtain the block copolymerization elastomer.
3. The method for preparing a block copolymer elastomer according to claim 2, wherein the first anionic polymerization conditions include: carrying out polymerization reaction under inert atmosphere, wherein the polymerization reaction temperature is 35-55 ℃, the reaction pressure is 0.2-0.4MPa, the reaction time is 5-15min, and the initiator is organic lithium;
the second anionic polymerization conditions include: carrying out polymerization reaction under inert atmosphere, wherein the polymerization reaction temperature is 35-55 ℃, the reaction pressure is 0.2-0.4MPa, and the polymerization reaction time is 10-30 min.
4. The method for producing a block copolymer elastomer according to claim 3, wherein the organolithium is at least one selected from the group consisting of n-butyllithium, sec-butyllithium and tert-butyllithium.
5. The method for preparing a block copolymer elastomer according to claim 2, wherein the inert solvent is one or more selected from C5-C8 alkane or C5-C8 cycloalkane.
6. A modified asphalt, comprising the block copolymer elastomer of claim 1 and an asphalt base having a designation of 100# -200 #.
7. The process for producing modified asphalt according to claim 6, which comprises the steps of: and melting the asphalt matrix, adding the block copolymer elastomer, rubber powder and filler, and mixing for reaction to obtain the modified asphalt.
8. The method for preparing modified asphalt according to claim 7, wherein the mass ratio of the asphalt matrix to the block copolymer elastomer, the rubber powder and the filler is 60-70:5-10:10-20: 10-15.
9. The method for preparing modified asphalt according to claim 7, wherein the melting temperature is 160-180 ℃, the mixing reaction time is 5-8h, and the mixing reaction temperature is 160-180 ℃.
10. Use of the modified asphalt of claim 6 in the fields of waterproofing materials and road surface applications.
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Citations (6)
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